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Late TM olefin polymerization Catalysts

Late TM olefin polymerization Catalysts. Why develop late TM polymerization catalysts ? increased functional group tolerance (copolymerization with certain polar comonomers) decreased air sensitivity (easier to handle)

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Late TM olefin polymerization Catalysts

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  1. Late TM olefin polymerization Catalysts Why develop late TM polymerization catalysts ? • increased functional group tolerance (copolymerization with certain polar comonomers) • decreased air sensitivity (easier to handle) • may reduce costs and environmental impact by using a cheaper metal (e.g. Fe) • unknown territory  could turn out to be better catalysts  may give polymers with different properties A - Jolly et al., Organometallics, 1997, 1511 B - Köhn et al., J. Chem. Soc., Chem. Commun., 2000, 1927 C- Brookhart et al., J. Am. Chem. Soc., 1998, 4049 - Brookhart et al., J. Am. Chem. Soc., 1998, 7143 - Gibson et al., J. Chem. Soc., Chem. Commun.,1998, 849 D- Ostoja et al., Angew. Chem., Int. Ed. Engl., 1985, 599 - Ostoja et al., Angew. Chem., Int. Ed. Engl., 1987, 63 E- Grubbs et al., Science, 2000, 460 F- Brookhart et al., J. Am. Chem. Soc., 1995, 6414 (DuPont Versipol Catalysts)

  2. Oligomerization vs Polymerization Catalysts

  3. Theoretical study of the Brookhart a-diimine catalysts Ziegler et al., J. Am. Chem. Soc., 1997, 6177. Bulky substituents in the 2,6-positions of the aryl rings on nitrogen have the following effects due to increased steric hindrance in the axial sites: • They destabilize the resting state of the catalyst (alkyl p-alkene complex), therefore lower the barrier for insertion. • They raise the energy barrier for chain termination.

  4. Chain walking mechanism for Pd or Ni diimine catalysts

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